WO1994007925A1 - Esterification de polymeres contenant des groupes carboxylate - Google Patents

Esterification de polymeres contenant des groupes carboxylate Download PDF

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Publication number
WO1994007925A1
WO1994007925A1 PCT/US1993/008851 US9308851W WO9407925A1 WO 1994007925 A1 WO1994007925 A1 WO 1994007925A1 US 9308851 W US9308851 W US 9308851W WO 9407925 A1 WO9407925 A1 WO 9407925A1
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recited
polymer
carboxylate
carbon atoms
ammonium
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PCT/US1993/008851
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English (en)
Inventor
Lewis Edward Manring
Michael Wendell Johnson West
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority claimed from US07/953,420 external-priority patent/US5324790A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to KR1019950701184A priority Critical patent/KR100264248B1/ko
Priority to EP93921679A priority patent/EP0663926B1/fr
Priority to BR9307446A priority patent/BR9307446A/pt
Priority to CA002145392A priority patent/CA2145392C/fr
Priority to DE69308156T priority patent/DE69308156T2/de
Priority to JP50911194A priority patent/JP3485922B2/ja
Priority to AU49298/93A priority patent/AU678994B2/en
Publication of WO1994007925A1 publication Critical patent/WO1994007925A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D157/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
    • C09D157/10—Homopolymers or copolymers containing elements other than carbon and hydrogen containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09D201/08—Carboxyl groups

Definitions

  • This invention concerns a process for esterifying a carboxylate containing polymer, by reacting selected ammonium or sulfoxonium salts of the carboxylate groups to effect esterification.
  • Carboxylate containing polymers are often used in products that are in water solution, dispersion, or emulsion, where the carboxylate groups may help solublize or stabilize such mixtures. Such polymers are used for coatings, adhesives, photo and thermal resists. However, once the water is removed from the polymer, it is often desirable ro somehow remove or convert the carboxylate groups into less polar moieties to reduce the effect of water on the resulting polymer (e.g., less water swell) , or to help coalesce the polymer into a uniform film by removing highly polar regions made up of carboxylate salts. The removal or conversion of carboxylate groups should take place when desired, after most of the water has been removed, and the process should preferably be efficient and proceed under relatively mild conditions.
  • This invention concerns a process for forming alkyl esters in polymers, comprising, maintaining a polymer containing carboxylate ions, whose counterions are esterifying ammonium or sulfoxonium ions at a temperature of about 0°C to about 200°C. It has been found that when the counterion (positive ion) of the carboxylate anion is an ammonium or sulfoxonium cation the salt of the cation is relatively stable in water, but efficiently esterifies the carboxylate group under relatively mild conditions in the substantial absence of water.
  • R a is alkyl or substituted alkyl
  • Z is a neutral compound which contains all of the ammonium or sulfoxonium ion except the group R a , and the starting carboxylate ion and final ester are bonded to a polymer.
  • None of the ammonium or sulfoxonium ions herein have a hydrogen atom attached to the atom that bears the positive charge.
  • all the useful ammonium ions herein are quaternary ammonium ions,, not protonated ammonia or primary, secondary or tertiary amines.
  • At least one of the groups attached to the atoms that bears the positive charge of the ammonium or sulfoxonium ion is an alkyl or substituted alkyl group.
  • the alkyl group, and phenyl group if present, may be substituted by a group which does not interfere with the esterification reaction.
  • the substituents may affect the reactivity of the onium ion towards esterification of the carboxylate group.
  • Suitable substituents include, but are not limited to, alkyl, aryl, ether, halo, ester, and amino.
  • the esterification reaction In the presence of large amounts of water or other strongly hydrogen bonding solvents such as alcohols, particularly the lower alcohols, the esterification reaction is slow or does not occur at detectable levels. It is believed that solvation of the ammonium or sulfoxonium ion and/or carboxylate ion by water or other hydrogen bonding compounds slows the esterification reaction. As the amount of water or other hydrogen bonding solvent decreases, the rate of the esterification reaction increases. It is difficult to remove the last traces of water from the carboxylate salts, since the water molecules (or other hydrogen bonding compounds) strongly solvate the carboxylate salts. Thus, it is believed that in most instances, the esterification reaction occurs in the "substantial absence" of water or other hydrogen bonding compounds, but the complete absence of water or other hydrogen bonding compounds is usually not attained while esterifying, and is probably not necessary.
  • the amount of water or other hydrogen bonding compounds that may be present during the esterification reaction depends on several interrelated factors, such as the inherent reactivities of the particular carboxylate ion and the particular ammonium or sulfoxonium ion, and the temperature at which the process is carried out. The higher any particular reactivity, or the higher the temperature, the more water may be present, and vice versa.
  • the particular combination of conditions necessary for esterification for any given system is readily determined (see below) , and some of these combinations are illustrated in the Examples herein.
  • the inherent reactivity of the carboxylate ion towards esterification by an ammonium or sulfoxonium ion is believed to be related to the pKa of the conjugate acid of the carboxylate ion.
  • the conjugate acid of the carboxylate ion has a pKa of 0 or more, more preferably 2 or more.
  • An important factor affecting the reactivity of the ammonium or sulfoxonium ion is whether the groups directly attached to the atom bearing the positive charge of the ion are relatively electron donating or electron withdrawing compared to an unsubstituted alkyl group.
  • electron withdrawing groups such as phenyl, and p-chlorophenyl will make the ion more reactive, and the more there are of such groups, the more reactive the ion will become.
  • Electron donating groups such as p-N,N-dimethylaminophenyl and ethoxymethyl will tend to slow the rate of reaction of the ion. Extremely reactive ions will tend to react with water to form alcohols and the corresponding neutral compound from the remainder of the ammonium or sulfoxonium ion.
  • Ammonium or sulfoxonium ions that are significantly unstable in the presence of water are not included in the present invention.
  • Ammonium or sulfoxonium ions that are too unreactive to esterify carboxylate ions in the substantial absence of water are also not included within the present invention.
  • the following simple test may be used to determine if any particular ammonium or sulfoxonium ion is included within the present invention:
  • a random copolymer (0.2 g) made of about 33 mole percent methacrylic acid and about 67 mole percent ethyl acrylate is mixed with 2 mL of water, and an equivalent amount of a basic salt of the ammonium or sulfoxonium ion such as the hydroxide or bicarbonate (see Examples 1 and 9) .
  • the polymer is allowed to dissolve by stirring 12-24 hrs at ambient temperature.
  • a film is made from the solution (if the polymer has precipitated from solution at this point, the ammonium or sulfoxonium ion is too reactive) of the polymer and an infrared spectrum is obtained, preferably without delay.
  • the polymer may be heated at up to 180°C under nitrogen for up to 48 hr. If the polymer is not at least 20 mole percent esterified at this point (as judged from the IR spectrum, or more exactly by an acid-base titration of the polymer) , the particular ammonium or sulfoxonium ion is not included herein.
  • the techniques used in this determination, including film formation, esterification, and measuring IR spectra, are illustrated in Examples 1 and 9.
  • Suitable types of cations that are useful herein include, but are not limited to, quaternary ammonium ions and sulfoxonium ions.
  • Specific cations that are useful herein include, but are not limited to R 1 R 2 R 3 R 4 N + where R 1 , R 2 and R 3 are independently alkyl containing 1 to 6 carbon atoms and R 4 is phenyl or alkyl containing 1 to 6 carbon atoms; and R 5 R 7 R 7 SO + where R 5 , R 6 and R 7 are independently alkyl containing 1 to 6 carbon atoms.
  • Preferred specific cations are tetramethylammonium, phenyltrimethylammonium, trimethylsulfoxonium, and (methoxymethyl)triethylammonium.
  • Another preferred esterifying cation is (YCH 2 ) 4 N + or (YCH 2 ) 3 SO + wherein each Y is independently selected from the group consisting of hydrogen, alkyl containing 2 to 10 carbon atoms, aryl containing 6-12 carbon atoms, aralkyl containing 7 to 20 carbon atoms, alkaryl containing 7 to 30 carbon atoms, alkaryl containing 7 to 30 carbon atoms and substituted with one to 5 esterifying ammonium or sulfoxonium ions, and alkyl containing 3 to 30 carbon atoms substituted with 1 to 5 esterifying ammonium or sulfoxonium ions, and provided that no more than one of Y is hydrogen.
  • esterifying cations which contain more than one esterifying ammonium or sulfoxonium ion are "poly- cations" (See the following paragraph.)
  • Useful groups Y include, but are not limited to, -CH 2 CH 3 , -CH(CH 3 ) 2 , n-C 5 Hn, -C(CH3)3, phenyl, CH C6H 5 , P-C6H 4 CH3 and
  • ammonium and sulfoxonium cations of the invention may be included in molecules that contain one or more cations per molecule. If more than one cation is present per molecule, the "poly-cation" may act a crosslinking agent if either the polymer and/or the "poly-cation” is tri- or higher functional.
  • an ammonium ion has the formula A3N + XN + A3, where each A is an alkyl group, and X is an alkylene group that is bound to (or connects) the two nitrogen atoms.
  • the polymer would become crosslinked, assuming each polymer chain has three or more esterified carboxylate ions.
  • the group (s) connecting the cations should preferably be more reactive towards esterification than the other groups bound to the cation atoms with the positive charges.
  • the polymer has more than two carboxyl(ate) groups and the ammonium or sulfoxonium ion is difunctional. This will cause crosslinking.
  • the ammonium or sulfoxonium ion is monofunctional .
  • the polymer has two carboxyl (ate) groups, preferably end groups, and the ammonium or sulfoxonium ion is difunctional. In this instance, chain extension via esterification takes place.
  • Any polymer containing carboxyl (ate) groups from which the ammonium or sulfoxonium salt may be formed is useful in the instant process. By containing carboxyl (ate) groups means that these groups are bound to the polymer.
  • the carboxylate salts of the ammonium or sulfoxonium ion may be formed by reacting the carboxylic acid form of the carboxyl (ate) group with a basic salt of the ammonium or sulfoxonium ion such as the hydroxide or bicarbonate. This is most conveniently done in a solvent which dissolves the basic ammonium or sulfoxonium salt and swells or dissolves the polymer and/or its ammonium or sulfoxonium salt.
  • water or the lower alcohols are usually suitable for polymers with relatively high carboxyl (ate) content.
  • Suitable types of polymers include, but are not limited to, acrylics, styrenics, polyesters, polyamides, polyimides, and polyolefins .
  • Especially preferred polymers are acrylic and styrenic polymers, and acrylic- styrenic copolymers .
  • carboxyl (ate) containing polymers suitable for use herein is known, and many of them can be bought.
  • acrylic polymer a polymer wherein 10 mole percent or more of the repeat units are acrylic acid and/or methacrylic acid and their derivatives .
  • acrylic derivatives herein are meant common derivatives of carboxylic acids such as, but not limited to, esters, amides, acyl halides, carboxylate salts (including ammonium and sulfoxonium ion containing carboxylates) and nitriles .
  • styrenic polymer a polymer wherein 10 mole percent or more of the repeat units are styrene, and/or alpha-methylstyrene and their derivatives.
  • derivatives are meant substituents on the phenyl ring such as methyl, halo, amino and carboxyl (ate) .
  • a polymer may contain a combination of acrylic and styrenic monomers.
  • the esterification process is carried out at a temperature of about 0°C to about 200°C, preferably about 15°C to about 150°C and most preferably about 25°C to about 130°C. The higher the temperature the faster the esterification reaction will proceed.
  • the polymer should be stable at the process temperature, and if the polymer is sensitive to oxygen at higher temperatures, an inert atmosphere, such as nitrogen, can be used.
  • Carboxylate containing polymers are used in such coatings, particularly when the solvent is water based.
  • the carboxylate groups in these polymers tend to make the polymers water soluble or at least help stabilize dispersions or emulsions of the polymers in the water.
  • Carboxylate containing polymers may also be used as surfactants for stabilizing emulsions of other polymers.
  • these carboxylate groups tend to retard the coalescence of less polar polymers of the coating, and also usually make the coating itself more water sensitive.
  • the carboxylate group could be converted to less polar groups.
  • the instant process does that by converting the carboxylate groups to the less polar, less hygroscopic, ester grouping, while not affecting the carboxylate group before the coating is applied, since a large amount of water is then present.
  • the esterification can be done under relatively mild conditions after the coating is substantially dry, the temperature required being dependent principally on the onium ion present, and the rate of reaction that is needed. If an ammonium or sulfoxonium ion is used which is di- or higher functional the resulting coating, after esterification, may be crosslinked. This is sometimes desirable, since crosslinking often increases hardness and improves solvent resistance.
  • This invention also includes an aqueous based coating composition which comprises polymeric carboxylate groups wherein the counterion is an esterifying onium ion. All of the preferred compositions and preferred conditions described above for the esterification process apply also to this coating composition.
  • MAA methacrylic acid
  • TEPAOH triethylphenylammonium hydroxide
  • TMPAOH trimethylphenylammonium hydroxide
  • TMPAOH was prepared by addition of excess silver oxide to a solution of trimethylphenylammonium bromide in methanol.
  • concentration of TMPAOH (1.1 molar) was determined by dilution in water and titration with HC1 (phenolphthalien end point) .
  • the copolymer used in examples 1-10 contains 66% ethyl aerylate (EA) and 33% methacrylic acid (MAA) .
  • the initial copolymer (a suspension in water, 29.7% solids) has a molecular weight of >500,000.
  • An FTIR of the initial polymer (cast on CaF2 from methanol) shows relevant bands at 1735 cm -1 (ethyl ester) , 1705 cm -1 (carboxylic acid) and 3100-3500 cm -1 (OH from water and carboxylic acid) .
  • EXAMPLE 1 EXAMPLE 1
  • the carboxylate CO stretch of the neutralized polymer (film cast on CaF 2 from water) shifted from 1705 cm -1 to 1575 cm -1 .
  • IR absorbance from 3100-
  • 3500 cm -1 is due to water retained in the ionic polymer.
  • the IR also contained a shoulder at 3030 cm -1 due to the aromatic C-H groups in the TMPA cation.
  • EXAMPLE 2 A film similar to the one described in Example 1 was heated to 120°C in an FTIR instrument. Complete conversion of the TMPA-carboxylate to methyl ester occurred before the apparatus reached 120°C.
  • EXAMPLE 3 A film similar to the one described in Example 1 was heated to 100°C in an FTIR instrument. Complete conversion of the TMPA-carboxylate to methyl ester occurred in ⁇ 12 ins . The ester absorbance increased from 0.74 absorbance units to 1.14 absorbance units, consistent with complete conversion of the TMPAOH neutralized carboxylates to methyl ester groups . 25
  • EXAMPLE 4 A film similar to the one described in Example 1 was heated to 80°C in an FTIR instrument. The apparatus required about 5 mins . to heat from room temperature to 80°C and ⁇ 70% of the TMPA-carboxylate is converted to methyl ester in ⁇ 20 mins. The ester absorbance increased from 0.5 absorbance units to 0.7 absorbance units, consistent with complete conversion of the reacted TMPAOH neutralized carboxylates to methyl ester groups.
  • EXAMPLE 5 The TMPAOH neutralized EA/MAA copolymer solution described in Example 1 was heated to 100°C (boiling water) for 30 mins. under conditions where the solvent could not evaporate. A film of the heated solution was cast on CaF 2 - The carboxylate CO stretch at 1575 cm -1 had not changed in intensity relative to the unheated solution.
  • This example demonstrated that the cationic esterification described in Examples 1-4 is preceded by film drying. Therefore, the aqueous polymer solution will have excellent shelf life and the esterification will not occur until the water is substantially removed.
  • EXAMPLE 6 A film similar to the one described in Example 1 was left a room temperature for 8 days. FTIR analysis indicated no conversion of the TMPA-carboxylate to methyl ester.
  • EXAMPLE 7 A film similar to the one described in Example 1 was placed under vacuum for 4 days at room temperature. During this period, - 40% of the TMPA-carboxylate is converted to methyl ester. The ester absorbance increases from 0.23 absorbance units to 0.27 absorbance units, consistent with complete conversion of the reacted TMPAOH neutralized carboxylates to methyl ester groups .
  • TMPAOH could be converted to trimethylphenyl- ammonium bicarbonate by passing CO 2 through the TMPAOH solution. It is likely bicarbonate solutions will be more stable than the hydroxides. Furthermore, under normal storage conditions it is possible that TMPAOH will be converted to the bicarbonate. 5
  • TMSOOH was prepared by addition of excess silver oxide to a solution of trimethylsulfoxonium iodide (Aldrich) in water. The concentration of TMSOOH
  • the carboxylate CO stretch of the TMSOOH neutralized polymer (film cast on CaF 2 from water) shifted from 1705 cm -1 to 1575 cm" 1 .
  • EXAMPLE 11 (Methoxymethyl)triethylammonium chloride was made by addition of 40 g triethylamine to 25 g of chloro- methyl methyl ether in 130 mL dichloromethane. A 7.8 g portion of the resulting salt (dried under vacuum) was reacted in 40 mL water with 5.6 g silver oxide to produce after filtration a solution of (methoxymethyl) - triethylammonium hydroxide, 0.92 M. The copolymer of Examples 1-10 (193 mg of a 30% solids mixture) was diluted by 1 mL water and neutralized with 238 mL of the hydroxide solution. A film was cast on a CaF 2 window, and IR showed the carboxylate band at about 1575 cm" 1 was comparable in absorbance to the ester band at
  • a paint was made from a combination of a commercial latex, ICI Neocryl A-640, 6.004 g, (believed to be a carboxyl containing acrylic-styrene resin) with a solution of coalescing agent and plasticizers (0.9547 g taken from a solution of 13.45 g l-butoxy-2-propanol, 1.5529 g dibutyl phthalate, and 0.0253 g triethylamine) , by titrating 1 gram of the resulting mixture with the bis-hydroxide solution described above (4.75 g required) .
  • Example 14 An analogous paint to that of Example 14 was made from the corresponding 1,3-bis (bromomethyl)benzene, i.e., the meta isomer. The corresponding paint was also crosslinked, showing a swelling of 1.51 +/- 0.03 times in methylene chloride.
  • EXAMPLE 16 Diisopropylethylamine was reacted with 1,4-bis- (bromomethyl) enzene to form the bis-quaternary salt. The recrystallized product was converted to its bis- hydroxide form, and used to neutralize Neocryl A640 as in Example 1 . A film was baked at 120°C for 20 minutes, showing a diameter swell factor in dichloromethane of 1.85, decreasing to 1.81 +/- 0.02 after a further 20 minutes at 120°C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Procédé d'estérification d'un polymère contenant des groupes carboxyl(ate) selon lequel on maintient le polymère à une température comprise entre 0 °C et 200 °C, le contre-ion destiné aux groupes carboxylate étant un ammonium sélectionné ou des ions sulfoxonium. Ces procédés sont utiles pour préparer des films et des revêtements améliorés, plus particulièrement des revêtements pour voitures.
PCT/US1993/008851 1992-09-29 1993-09-23 Esterification de polymeres contenant des groupes carboxylate Ceased WO1994007925A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
KR1019950701184A KR100264248B1 (ko) 1992-09-29 1993-09-23 카복실레이트 함유 중합체의 에스테르화
EP93921679A EP0663926B1 (fr) 1992-09-29 1993-09-23 Esterification de polymeres contenant des groupes carboxylate
BR9307446A BR9307446A (pt) 1992-09-29 1993-09-23 Processo formação de alquil ésteres em polímeros e composição de revestimentos de base aquosa
CA002145392A CA2145392C (fr) 1992-09-29 1993-09-23 Esterification de polymeres renfermant des carboxylates
DE69308156T DE69308156T2 (de) 1992-09-29 1993-09-23 Veresterung von carboxylatgruppen enthaltenden polymeren
JP50911194A JP3485922B2 (ja) 1992-09-29 1993-09-23 カルボキシラート含有ポリマーのエステル化
AU49298/93A AU678994B2 (en) 1992-09-29 1993-09-23 Esterification of carboxylate containing polymers

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/953,420 US5324790A (en) 1992-09-29 1992-09-29 Esterification of carboxylate containing polymers
US07/953,420 1992-09-29
US08/124,781 1993-09-21
US08/124,781 US5463182A (en) 1992-09-29 1993-09-21 Esterification of carboxylate containing polymers

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EP (1) EP0663926B1 (fr)
JP (2) JP3485922B2 (fr)
KR (1) KR100264248B1 (fr)
AU (1) AU678994B2 (fr)
BR (1) BR9307446A (fr)
CA (1) CA2145392C (fr)
DE (1) DE69308156T2 (fr)
ES (1) ES2098059T3 (fr)
MX (1) MX9306028A (fr)
WO (1) WO1994007925A1 (fr)

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JP2716361B2 (ja) * 1994-02-16 1998-02-18 株式会社アドバンス 生体用プリント電極
US6143835A (en) * 1998-04-03 2000-11-07 Solutia Inc. Polyacrylonitrile polymer treatment

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Publication number Priority date Publication date Assignee Title
DE2166551B2 (de) * 1970-12-26 1981-05-07 Asahi Kasei Kogyo K.K., Osaka Copolymerisate mit äthylenisch ungesättigten Seitenketten und deren Verwendung
EP0159643A2 (fr) * 1984-04-26 1985-10-30 Bayer Ag Procédé de fabrication de produits d'alkoxylation d'acides carboxyliques organiques renfermant des groupes hydroxyles.

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DE69308156T2 (de) 1997-06-26
CA2145392A1 (fr) 1994-04-14
MX9306028A (es) 1994-07-29
JPH08501822A (ja) 1996-02-27
EP0663926A1 (fr) 1995-07-26
AU4929893A (en) 1994-04-26
BR9307446A (pt) 1999-06-01
ES2098059T3 (es) 1997-04-16
AU678994B2 (en) 1997-06-19
KR100264248B1 (ko) 2000-08-16
CA2145392C (fr) 2005-02-08
DE69308156D1 (de) 1997-03-27
KR950703584A (ko) 1995-09-20
JP3485922B2 (ja) 2004-01-13
US5463182A (en) 1995-10-31
EP0663926B1 (fr) 1997-02-12
JP2003327897A (ja) 2003-11-19

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